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Publication numberUS3684771 A
Publication typeGrant
Publication dateAug 15, 1972
Filing dateMar 3, 1971
Priority dateMar 3, 1971
Also published asCA966245A1
Publication numberUS 3684771 A, US 3684771A, US-A-3684771, US3684771 A, US3684771A
InventorsBraun Robert A
Original AssigneeDu Pont
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
Polyesters with substituted amine end groups
US 3684771 A
Abstract
Polyesters represented by the general structure USEFUL AS FILM-FORMERS IN COATING COMPOSITIONS WHEREIN G may be isocyanate, amino, carbamate, or urea groups, and Q is a dicarboxylic acid - diol or polylactone polyester chain.
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United States Patent Braun [45] Aug. 15, 1972 POLYESTERS WITH SUBSTITUTED 3,367,956 2/1968 Hennig'etal. ..260/453 AMINE END GROUPS Inventor: Robert A. Braun, Rochester, NY.

Assignee: E. l. du Pont de Nemours and Company, Wilmington, Del.

Filed: March 3, 1971 Appl. No.: 120,769

Related US. Application Data Continuation-in-part of Ser. No. 776,823, Nov. 18, 1968, abandoned.

References Cited UNITED STATES PATENTS 8/ 1965 Wagner 260/ 77.5

3,591,560 7/1971 Wagner et a1. ..260/77.5

Primary Examiner-William H. Short Assistant Examiner-E. Nielsen Attorney-Fred F. Butzi [57] ABSTRACT Polyesters represented by the general structure 0 H II G-R-N-C H II N-RNCQ G-R-N-O H ll M 0 useful as film-formers in coating compositions wherein G may be isocyanate, amino, carbamate, or urea groups, and Q is a dicarboxylic acid diol or polylactone polyester chain.

3 Claims, No Drawings POLYESTERS WITH SUBSTITUTED AMINE END GROUPS CROSS-REFERENCE TO RELATED APPLICATIONS This application is a continuation-in-part of application Ser. No. 776,823, filed Nov. 18, 1968, and now abandoned.

STATEMENT OF THE INVENTION This invention relates to polyesters. It is more particularly directed to polyesters represented by the structure where G can be -NCO, -NH

or -CH CH NHNH and R, and R can be hydrogen, alkyl of one through six R can be alkylene of two through ten carbon atoms, phenylene, tolylene,

| OCH where D can be alkyl of one through 18 carbon atoms;

X and Y can be phenylene or alkylene of two through 18 carbon atoms; and

n is a number 10-500.

UTILITY The polymers of the invention are useful as film-formers in coating compositions, particularly when combined with a second polymer having complementary reactive groups. Illustrative of such second polymers are heat reactive phenolics, polyglycidyl ethers and esters, polyisocyanate resins, butylated urea/formaldehyde resins and melamine/formaldehyde/alkanol resins.

The polymers of the invention can be cured as filmformers by mixing from about 55 to about 95 parts of the polymer with from about 5 to 4.5 parts of the second complementary polymer, in a suitable solvent. This solution can then be used directly to give clear coatings or it may be pigmented as desired.

The coating composition can be applied conventionally and is preferably then baked for from about 10 to 30 minutes at 200C.

The polymers of the invention are also useful as aids for dispersing solid particles in organic liquids. They are especially useful as aids for dispersing pigments in organic liquids. Illustrative of the pigments which can be dispersed are titanium dioxide, carbon black, zinc oxide, lead titanate, potassium titanate, antimony oxide, lithopone, phthalocyanine blue, toluidine red, quinacridone and the like.

Pigment dispersions made with polymers of the invention are remarkably resistant to flocculation, which gives the paints into which dispersions are incorporated higher initial gloss, better hiding and tinting strength, and makes them resistant to color drift and gloss loss. These pigment dispersions can also be used satisfactorily with many more diverse types of paints than conventional pigment dispersions. Moreover, a dispersion made with a polymer of the invention can have a significantly higher pigment content, while retaining the same degree of fludidity, than when conventional aids are used.

The polymers of the invention can be used as pigment dispersing aids by dissolving from 0.001 to about 2.00 grams of polymer per square meter (Measured by the Brunauer, Emmett and Teller nitrogen adsorption method described on page 30 of Colloidal Disperdispersion is to be incorporated. Illustrative of organic 5 liquids which can be used are aliphatic and aromatic hydrocarbons, ethers, esters, ketones, alcohols, and mixtures of these.

An appropriate amount of pigment is then added to this solution, which is then subjected to shear, as by sand-grinding, or ball-milling, to deagglomerate and disperse the pigment. This pigment dispersion or millbase can be then added directly to a paint.

Polymers of the invention preferred for use as pigment dispersing aids are those of formula 1 where R is alkylene of two through ten carbon atoms, D is alkyl of three through ten carbon atoms and n is 10 through 200. Especially preferred are those whose preparation is shown in Examples 1, 3, 6, 7 and 8.

The polymers of the invention are also useful for dispersing magnetic oxides such as iron oxide and chromium dioxide in compositions used to prepare magnetic tape. Use of 05-10 percent, by weight of such a composition, of a polymer of the invention promotes wetting of the oxide, improves adhesion of the composition to the tape substrate and improves the tape s magnetic properties.

PREPARATION OF THE POLYMERS L Jim In this equation, R is an alkylene group.

l. Polymerizing a lactone such as propiolactone, caprolactone or pivalolactone.

The hydroxyl-terminated polyester can be prepared 2. Condensing a glycol and a dibasic acid in the presence of a mono-alcohol. The formation of polyesters capped at both ends with hydroxyl groups should be minimized. This can be done by controlling the stoichiometry of the reaction so that the acid number and the hydroxyl number of the polyester are approximately equal.

3. Condensing a hydroxy acid in the presence of a small amount of mono-alcohol.

Illustrative of these reactions are These reactions are described in greater detail in Preparative Methods of Polymer Chemistry, Sorenson and Campbell, Interscience Publishers, Inc. New York, NY. (1961), Pplll-l27 and 242-247 and Polyesters and Their Applications, Bjorksten Research Laboratories, Inc., Reinhold Publishing Corp., New York, N.Y. (1956).

The polyester thus prepared is dissolved in an inert liquid like anhydrous benzene. The tri-isocyanate is then added, together with about 0.1 percent (by weight) of dibutyl tin dilaurate. This mixture is heated for about 1 hour at 130C. The resulting product can be isolated by stripping off the solvent at C. and a pressure of 20 mm.

Modifications can be made, if desired, by reacting the product, without isolation, with compounds having active hydrogen atoms, to give other polymers of the inventionlllustrative of such compounds are:

Active hydrogen compound Resulting G group @otmrm To make such a modification, 1-2 moles of reactant for each mole of the polyester-isocyanate product is added to the polyester-isocyanate reaction mass, together with another 0.1% (by weight) of dibutyl tin dilaurate. This mixture is then heated for about one hour at 80- 1 30C.

The resulting polymercan be isolated from the reaction mass by heating it at 100C. for 1 hour at 20 mm. pressure to strip off volatiles.

The physical properties of the polymers of the invention thus prepared range from viscous liquid to friable solid. They are soluble in common organic liquids such as toluene, ethyl acetate, tetrahydrofuran, acetone, hexane, cyclohexane and dimethylfonnamide.

EXAMPLES The following examples are submitted so that the invention may be more readily understood and practiced.

Those skilled in the art will no doubt be able to compose numerous variations on their central theme, such as the attachment of innocuous substituents. It is naturally considered that these variations are a part of the invention.

In the Examples all parts are by weight unless otherwise indicated.

EXAMPLE 1 Fifty-nine and two tenths'parts of butyl alcohol initiated polycaprolactone (molecular weight 2960) were dissolved in 100 parts of reagent grade benzene. To this were added, with stirring and in a nitrogen atmosphere, 15.3 parts of a 75 percent solution of O CN(CH2)0N[11NH(CH2)o-NCO)]2' in cellosolve acetate. One-tenth part of dibutyl tin dilaurate catalyst was added and the mixture heated at 80C. for 1 hour.

The solvent was stripped off at 100C. and 20 mm. of 60 pressure to give a waxy solid having the structure EXAMPLE 2 To the product of Example 1, before stripping, were added 5 parts of absolute ethanol and 01 part of dibu- 5 tyl tin dilaurate. This mixture was refluxed for l hour.

Solvent was removed by stripping at 100C. and mm. of pressure. The product was a waxy solid having the structure EXAMPLE 3 For thirty minutes, ammonia gas was bubbled through the final reaction mass (before stripping) of Example 1. Excess ammonia and solvent were then removed by stripping at 100C. and 20 mm. of pressure to give a waxy solid having the structure To the product of Example 1, before stripping, were added.3.5 parts of anhydrous hydrazine. The mixture was heated at C. for 1 hour.

Excess hydrazine and solvent were removed by stripping at C. and 20 mm. of pressure to give a waxy solid having the structure To the product of Example I, before stripping, were added 3 parts of dimethylol propionic acid and 0.1 part of dibutyl tin dilaurate. The mixture was heated for '1 hour at 80C.

7 8 This was then cooled and partially stripped to t o 0 remove some solvent. Seventy parts of acetone were \rwmnfi-d-fiQmA-rrm'i added and unreacted dimethylol propionic acid was fil- A f H 0 N--CH2N- tered off. The filtrate was then stripped at 100C. and H30 A 20 mm. of pressure to give a waxy solid having the 5 H structure /N(CHz):Nt g(CH,7-HN(|3 6 oHlon 0 H30 3 1) EXAMPLE 6 where 1 2 1 b To the product of Example l,before stripping, were 5 2 5 1 flfijf fff of through 0 car on atoms added 3 parts of water and 0.1 part of dibutyl tin dilaurate. The mixture was heated for one hour at 80C.

Excess water and solvent were then removed by stripping at 100C. and 20 mm. of pressure to give a waxy solid having the structute V A120 tone (molecular weight 2960) were dissolved in 150 I parts of anhydrous ethylene glycol dimethyl ether. To CH2- 0-0-( CHz this were added 14.8 parts of Desmodur N75. This or A solution was mixed and 0.2 part of dibutyl tin dilaurate 0 was added. The mixture was then heated for 2 hours at t g fl l 80C. l1

To this were then added 13.9 parts of l2-hydroxy Q can be stearic acid, together with 0.1 part of dibutyl tin dilau- I rate and parts of anhydrous ethylene glycol dimethyl J 01) ether. The mixture was heated at 80C for 3 hours and or n then stripped at 100C. and 20 mm. of pressure to give I- 0"I a waxy solid having the structure 50 P;J 0D

. WWW.- .&. H l H H where HO 0 Z? 0 T /T o D can be alkyl of one through 18 carbon atoms;

(CHmCHi ;g X and Y can be phenylene or alkylene of two 2)5 s A through 18 carbon atoms; Hooo(oH2 t :-0oN(oHQ-No and m I A H n is anumber 10500.

' 2. The polymeric material of claim 1 wherein R is alkylene of two through ten carbon atoms, D is alkyl of lJ three through ten carbon atoms and n is 10 through L. /s |-2o t 200.

' 4 3. The polymeric material of claim 1 having the for- EXAMPLE 8 mula The procedure of Example 4 was followed, except OCMCHZMHNA i t: that 2 parts of N,N-dimethylethylene diamine were I NWHMN Towfifil substituted for the hydrazine. 0 CN(CHz)HNt1 The product had the structure

Patent Citations
Cited PatentFiling datePublication dateApplicantTitle
US3201372 *Dec 5, 1963Aug 17, 1965Bayer AgBiuret polyisocyanate based polyurethanes
US3367956 *Apr 1, 1964Feb 6, 1968Bayer AgPreparation of biuret polyisocyanates
US3591560 *Jul 31, 1968Jul 6, 1971Bayer AgPolyurethanes from biuret-containing organic polyisocyanates
Referenced by
Citing PatentFiling datePublication dateApplicantTitle
US3905937 *Nov 9, 1973Sep 16, 1975Du PontColor concentrates
US3976622 *May 19, 1975Aug 24, 1976Bayer AktiengesellschaftPolyurethanes
US3988288 *Aug 21, 1974Oct 26, 1976Kawakami Paint Mfg. Co. Ltd.Powder paint
US4001164 *Jul 2, 1975Jan 4, 1977E. I. Du Pont De Nemours And CompanyA colorant; film-former; carrier
US4001171 *Jun 26, 1975Jan 4, 1977E. I. Du Pont De Nemours And CompanyPolymeric fibers containing color concentrates
US4026916 *Mar 15, 1976May 31, 1977E. I. Du Pont De Nemours & CompanyPolymerizing pivalolactone, nitrogen-containing initiator
US4102797 *May 3, 1976Jul 25, 1978Shell Oil CompanyAntioxidants
US4379914 *Dec 21, 1981Apr 12, 1983Exxon Research And Engineering Co.Terminated with a tert-containing diamine, used to neutralize organic or polymeric sulfonic acids
US4652388 *Mar 26, 1984Mar 24, 1987Gold Marvin HWater based dispersion; adhesive plasticizer and polymer
US4762752 *Sep 30, 1986Aug 9, 1988Byk-Chemie GmbhAddition compounds, suitable as dispersing agents, processes for their preparation, their use and solids coated therewith
US4820432 *Jul 24, 1987Apr 11, 1989Exxon Chemical Patents Inc.Lactone-modified, Mannich base dispersant additives useful in oleaginous compositions
US4866139 *Oct 7, 1986Sep 12, 1989Exxon Chemical Patents Inc.Lactone modified, esterified dispersant additives useful in oleaginous compositions
US4866140 *Oct 7, 1986Sep 12, 1989Exxon Chemical Patents Inc.Oil, fuel additives
US4866141 *Oct 7, 1986Sep 12, 1989Exxon Chemical Patents Inc.Lactone modified, esterfied or aminated additives useful in oleaginous compositions and compositions containing same
US4906394 *Oct 7, 1986Mar 6, 1990Exxon Chemical Patents Inc.Lactone modified mono-or dicarboxylic acid based adduct dispersant compositions
US4942213 *Nov 30, 1988Jul 17, 1990Byk-Chemie GmbhAddition compounds useful as dispersing agents and dispersion stabilizers, process for producing them, their use and solids coated therewith
US4943382 *Apr 6, 1988Jul 24, 1990Exxon Chemical Patents Inc.Lactone modified dispersant additives useful in oleaginous compositions
US4954276 *Aug 31, 1989Sep 4, 1990Exxon Chemical Patents Inc.Olefin polymer modified by an unsaturated dicarboxylic acid and a hydroxy-amide or hydroxy-ester compound; efficiency; crankcase oil additive
US4954277 *Aug 31, 1989Sep 4, 1990Exxon Chemical Patents Inc.Lactone modified, esterified or aminated additives useful in oleaginous compositions and compositions containing same
US4963275 *Apr 6, 1988Oct 16, 1990Exxon Chemical Patents Inc.Dispersant additives derived from lactone modified amido-amine adducts
US4971711 *Jan 9, 1989Nov 20, 1990Exxon Chemical Patents, Inc.Lactone-modified, mannich base dispersant additives useful in oleaginous compositions
US5032320 *Feb 28, 1991Jul 16, 1991Exxon Chemical Patents Inc.Oil additives
US5100969 *Aug 18, 1989Mar 31, 1992Nippon Oil And Fats Company LimitedAcrylic ester polymers reacted with amine, dispersant crosslinks with paint film
US5187229 *Dec 13, 1991Feb 16, 1993Nippon Oil And Fats Company, Ltd.Pigment dispersing agent
US5399294 *Dec 27, 1990Mar 21, 1995Efka-Chemicals B.V.Dispersing agents, their use and solids coated therewith
US5425900 *Jun 25, 1992Jun 20, 1995Efka-Chemicals B.V.Dispersing agents, their use and solids coated therewith
US5508379 *Dec 21, 1994Apr 16, 1996Basf CorporationCarbamate-functional polyester polymer or oligomer and coating composition
US5532061 *Dec 21, 1994Jul 2, 1996Basf CorporationCarbamate-functional polyester polymer or oligomer having pendant carbomate groups
US5874197 *Sep 18, 1997Feb 23, 1999E. I. Du Pont De Nemours And CompanyThermal assisted photosensitive composition and method thereof
US5916985 *Sep 28, 1995Jun 29, 1999Lvmh RechercheFunctionalised polymers, method for synthesising same and use thereof as surfactants, particularly in cosmetic compositions such as nail varnish
US5958385 *Sep 28, 1995Sep 28, 1999Lvmh RecherchePolymers functionalized with amino acids or amino acid derivatives, method for synthesizing same, and use thereof as surfactants in cosmetic compositions, particularly nail varnishes
US7083674Sep 6, 2005Aug 1, 2006Toyo Ink Mfg. Co., Ltd.metal salt of a condensed azo pigment sulfonate; flowability and dispersion stability, high gloss
US7234398Jan 21, 2003Jun 26, 2007E. I. Du Pont De Nemours And CompanyPlanarizing element for thermal printing of color filter
US7276325Dec 29, 2005Oct 2, 2007E.I. Dupont De Nemours And CompanyUsing photosensitive copper conductive mixture of copper powder in binder; controlling particle sizes
US7303854Nov 6, 2003Dec 4, 2007E.I. Du Pont De Nemours And CompanyElectrode-forming composition for field emission type of display device, and method using such a composition
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US8748550Mar 12, 2010Jun 10, 2014Valspar Sourcing, Inc.Vinyl polymer wetting and dispersing agent
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USB590502 *Jun 26, 1975Mar 23, 1976 Title not available
USB592658 *Jul 2, 1975Mar 23, 1976 Title not available
EP0270126A2 *Dec 4, 1987Jun 8, 1988Byk-Chemie GmbHAddition compounds suitable as dispersants or as dispersion stabilizers, process for their preparation, their use and the solids coated therewith
EP0438836A1 *Dec 28, 1990Jul 31, 1991Efka-Chemicals B.V.Dispersants, use thereof and solids coated therewith
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Classifications
U.S. Classification560/159, 528/354, 528/274, 528/355, 252/62.54, 528/44, 528/48, 528/73, 528/272
International ClassificationC08G18/00, C08G18/28, C08G18/78, C08G18/42
Cooperative ClassificationC08G18/7831, C08G18/4266, C08G18/284
European ClassificationC08G18/78B4F, C08G18/42H, C08G18/28D5K